Bond Polarizability Model for Sum Frequency Generation at the Al2O3(0001)-H2O Interface

Mark Dellostritto, Jorge Sofo

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Sum Frequency Generation (SFG) is a powerful, surface-specific vibrational probe ideally suited to studying buried interfaces; however, insight from theory is often necessary to explain the microscopic origins of the spectral features. To calculate the SFG spectrum at an insulating solid/liquid interface, we develop a flexible polarizability model that takes local dipole interactions into account, rather than assuming additive polarizabilities. We use this model to calculate bond dipoles and polarizabilities that reflect the local geometry of the interface. We apply our method to the Al2O3(0001)-H2O interface, where we reproduce the experimental spectrum and show the two H stretching peaks come from solvent and surface modes separately, not from H2O molecules with different coordination numbers as previously thought. Our work therefore emphasizes the importance of treating both surface and solvent at the same level of theory for accurate spectroscopic calculations.

Original languageEnglish (US)
Pages (from-to)3045-3055
Number of pages11
JournalJournal of Physical Chemistry A
Volume121
Issue number16
DOIs
StatePublished - Apr 27 2017

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dipoles
liquid-solid interfaces
coordination number
Stretching
Molecules
Geometry
probes
Liquids
geometry
molecules
interactions

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry

Cite this

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abstract = "Sum Frequency Generation (SFG) is a powerful, surface-specific vibrational probe ideally suited to studying buried interfaces; however, insight from theory is often necessary to explain the microscopic origins of the spectral features. To calculate the SFG spectrum at an insulating solid/liquid interface, we develop a flexible polarizability model that takes local dipole interactions into account, rather than assuming additive polarizabilities. We use this model to calculate bond dipoles and polarizabilities that reflect the local geometry of the interface. We apply our method to the Al2O3(0001)-H2O interface, where we reproduce the experimental spectrum and show the two H stretching peaks come from solvent and surface modes separately, not from H2O molecules with different coordination numbers as previously thought. Our work therefore emphasizes the importance of treating both surface and solvent at the same level of theory for accurate spectroscopic calculations.",
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Bond Polarizability Model for Sum Frequency Generation at the Al2O3(0001)-H2O Interface. / Dellostritto, Mark; Sofo, Jorge.

In: Journal of Physical Chemistry A, Vol. 121, No. 16, 27.04.2017, p. 3045-3055.

Research output: Contribution to journalArticle

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